Method of forming ribbed battery separators

ABSTRACT

Ribs are formed on a nonwoven mat to produce a battery separator. The ribs are formed by extruding a foamed polymer onto the nonwoven mat by extruding the foamed polymer through a multihole die as the nonwoven mat follows an arc passing over a mat backup plate. After the ribs have been extruded and the foamed polymer is still soft, the nonwoven mat with the extruded ribs may be passed through a fixed gap such as a pair of calender rolls to produce a battery separator of uniform thickness.

United States Patent 1191 1451 Nov. 20, 1973 Morgan [54] METHOD OF FORMING RIBBED BATTERY 2,539,690 1/1951 Boom 156/178 SEPARATORS 3,565,737 2/1971 bcfevre..... 156/244 3,565,741 2/1971 Jaray 161/60 Inventor: Walter g y 3,113,061 12/1963 Donaldson 156/178 3,379,811 4/1968 Hartmann et a].... 264/176 [73] Assgnee' f gi l tg f g 3,509,009 4 1970 Hartman 156/181 9 s [22] Filed: July 16, 1971 Primary ExaminerAlfred L. Leavitt Assistant Examiner-Caleb Weston [21] Appl' 163306 Attorney-Thomas B. McCulloch et al.

[52,] 11.8. C1. 156/244, 136/145, 1l3566/114788, 57 ABSTRACT [51] Int Cl 01m /3/02 Ribs are formed on a nonwoven mat to produce a bat- [58] Fieid 179 180 tery separator. The ribs are formed by extruding a 156/181 136/145 foamed polymer onto the nonwoven mat by extruding 6 264/176 the foamed polymer through a multi-hole die as the nonwoven mat follows an are passing over a mat [56] References Cited backup plate. After the ribs have been extruded and UNITED STATES PATENT the foamed polymer is still soft, the nonwoven mat S with the extruded ribs may be passed through a fixed 3,084,091 4/1963 Volkman et 136/148 gap uch as a of calender rolls to produce a bati; h t at a] tery separator of uniform thickness. 3,556,851 1/1971 Douglas et a1. 136/145 X 5 Claims, 5 Drawing Figures Patented Nov. 20,1973 I 3,773,590

WALTER A. MORGAN, I N VEN TOR.

ATTORNEY.

METHOD OF FORMING RIBBED BATTERY SEPARATORS BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is directed to a nonwoven battery separator. More particularly, the present invention relates to a method of forming ribs on a battery separator which comprises extruding a foamed polymer onto 1 the nonwoven mat through a multihole die as the nonwoven mat passes over a mat backup plate.

2. Prior Art Battery separators made from polyolefins, specficially polypropylene, are illustrated in the following U.S. Pat. Nos.: 3,002,040; 3,092,438; 3,026,366; 3,045,058; 3,055,966; 3,084,091; 3,216,864; 3,314,821; 3,351,495; 3,354,247.

SUMMARY OF THE INVENTION The present invention is directed to nonwoven mats composed of randomly laid fibers having an average diameter of less than microns and having a maximum pore size of less than 40 microns which is suitable as a battery separator having extruded thereon ribs of a foamed polymer. The battery separators of the present invention exhibit improved abrasion resistance, compressive strength, stiffness perpendicular to the ribs, and thickness uniformity over the materials previously used as battery separators. The battery separators of the present invention arepreferably produced by a melt-blowing process which comprises extruding a polymer such as polypropylene, polystyrene or mixtures thereof, through a die into a heated air stream which attenuates the fibers to produce fine fibers and collecting these fibers on a moving screen in the form ofa mat. The nonwoven mat is then compacted to produce the nonwoven structure of the present invention which is usable as a battery separator. More specifically, the present invention is directed to forming ribs on such a nonwoven structure by extruding a foamed polymer onto the nonwoven mat as it passes directly beneath a multi-hole die as the nonwoven mat follows an are as it passes over a backup plate. The purpose of extruding the foamed polymer as the nonwoven mat passes over the arc of the web backup plate is to compensate for the shrinkage in the foamed polymer as it solidifies. While the rib material is still soft, the nonwoven mat with extruded ribs may be passed between a pair of calender rolls having a fixed gap so that the finished battery separator has the desired and uniform overall thickness.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of the overall melt-blowing process;

FIG. 2 is a cross-sectional view of a die used in the melt-blowing process;

FIG. 3 is a schematic view of extruding a foamed polymer onto a nonwoven mat to produce a batter separator;

FIG. 4 is a schematic view of a battery separator hav' ing extruded ribs as extruded; and

FIG. 5 is a schematic view of a battery separator having extruded ribs and pressed.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring to FIG. 1 of the drawings, polypropylene, which is the preferred material although polystyrene or mixtures of polystyrene and polypropylene may be used, is introduced into a pellet hopper l of an extruder 2. The polypropylene used in the present invention has either been thermally treated before being introduced 0 into the extruder 2 or is thermally treated in the extruder 2 and/or die head 3. According to the present invention, the polypropylene is added into the hopper l and then is heated in extruder 2 at temperatures in excess of 600F. and preferably within the range of 620 to 800 F. After thermal treatment, the polypropylene is forced through the extruder 2 by a drive motor 4 into the diehead 3. The die head 3 may contain a heating plate 5 which may also be used in the thermal treatment of the polypropylene before it is melt-blown. The polypropylene is then forced out a row of die openings 6 in the die head 3 into a gas stream which attenuates the polypropylene into fibers 7 which are collected on a moving collecting device 8 such as a drum 9 to form a continuous mat 10. The gas stream which attenuates the polypropylene is supplied through a gas jet 11 and 12, respectively. These gas slots 11 and 12 are supplied with a hot gas, preferably air, by gas lines 13 and 14, respectively.

The melt-blowing process may be further understood by considering the details of the die head 3 which is set forth in cross-section in FIG. 2. The polypropylene is introduced into the back of the die plates 15 and 16 through an inlet 17. The polypropylene then goes into a chamber 18 between the upper and lower die plates 15 and 16, respectively. The facing of the die plate 16 has milled grooves 19 which terminate in the die openings 6. It is understood, of course, that the mill grooves may be in the lower die plate 16, in the upper die plate 15, or grooves may be milled in both plates 15 and 16. An upper gas cover plate 20 and a lower gas cover plate 21 are connected to the upper die plate in lower die plate 15 and 16, respectively. The hot gas is supplied by inlets 22 in upper air plate 20 and lower inlet 23 in lower gas plate 21. Suitable baffling means (not shown) may be provided in both the upper air chamber 24 and lower air chamber 25 to provide a uniform flow of air through the gas slots 26 and 27, respectively. As shown in FIG. 2, the rear portion of the die head 3 may contain heating means 5 for heating both the polymer and air in the die head 3.

The gas flow is controlled so that the fibers as they are attenuated do not come into contact one with the other which results in rope and fiber bundles. The gas, preferably air, is heated and the flow controlled to produce very fine fibers (less than l0 microns). Suitable polypropylene mats have been obtained at air -rates between 0.7 and 4 p'oundslminute'and polypropylene fibers are attenuated in the gas stream at those rates such that their average diameter is between one to about 10 microns.

.The fibers are collected as a self-supporting mat on a collecting device such as a rotating drum at distances of about I to 18 inches from the die openings. Preferably a mat of self-bonded fibers is collected at a distance between 3 to 8 inches. A self-bonded? mat as used herein means that the mat is a coherent, integral structure capable of withstanding normal handling such as winding, unwinding, cutting, pressing, calendering, etc., without losing its essential mat-like character. In most mats used in the present invention, some thermal bonding occurs. The mat produced by the melt-blowing process is produced so as to have a basis weight of between 60 and 500 grams/square meter. The thickness of the nonwoven mat may vary between 20 and 200 mils.

To produce a battery separator from the nonwoven mat produced by the melt-blowing process, the mat must be compacted to obtain the desired thickness and porosity, as well as the mechanical properties of strength and abrasion resistance. The nonwoven mat is compacted to a thickness of between and 40 mils to be useful as a battery separator in most batteries. Compacting is preferably carried out by a thermal compacting operation utilizing calender rolls or a press to obtain the nonwoven mat of fixed thickness.

Referring to FIG. 3 of the drawing, a multi-hole die 30 is positioned over the non-woven mat as the mat 31 passes over a backup plate 32. The multi-hole die 30 is fed with molten polymer preferably containing a foaming agent. the polymer used to form the rib is preferably of the same polymer as used in making the nonwoven mat, for example if the nonwoven mat 31 is made of polypropylene fibers the polymer used to form the ribs is also of polypropylene. However, other thermoplastic polymers may be used to form the ribs. The foaming agent used may be one compatible with the particular polymer used to form the ribs. For example, suitable foaming agents are l,l '-azobisformamide (azodicarbonamide), p-toluene sulfonyl semicarbozide, 4,4- oxybis (benzene sulfonyl hydrazide) and when polypropylene is used 1,1 -azobisformamide (azodicarbonamide) is preferred. The polymer and foaming agent are introduced to a screw extruder (not shown) wherein the polymer is melted and forced into and through the multi-hole die 30 to extrude and desired number of ribs onto the nonwoven mat 31.

The multi-hole die 30 is positioned over the nonwoven mat 31 so that the axis of the line of holes in the die 31 is normal to the direction of mat motion and the hole spacing in the die 30 is equal to the desired rib spacing. Directly beneath the multi-hole die 30, the nonwoven mat 3] follows an are as it passes over the mat backup plate 32. The amount of curvature in the backup plate 32 will vary depending upon the specific polymer and foaming agent used and the extrusion tem peratures for producing the foamed polymer ribs. The purpose of the arc in backup plate 32 is to compensate for the shrinkage which takes place in the foamed polymer as it solidifies.

The nonwoven mat 31 is passed through fixed gap compacting calender rolls 33 and 34 before the foamed polymer is extruded onto the nonwoven mat 31. However, while the extruded polymer ribs are still soft, the nonwoven mat with the extruded ribs may be passed between a pair of calender rolls 35 and 36, which have a fixed gap so as to produce a finished battery separator having a uniform overall thickness.

The present invention will be further illustrated by the following specific examples which are given by way ofillustration and not as limitations on the scope of the invention.

EXAMPLE I Nonwoven polypropylene mats were produced by the melt-blowing process under the following conditions:

Resin 33.6 melt flow rate Die Temp. F. 580 Air Temp. F. 644 Polymer Rate gm/min 7.9 Air rate lbs./min. 1.27 Collector distance in. 6.0 RPM 1.0

The polypropylene fibers in the mats produced were of a diameter of 2 microns of less. The basis weight of mats so produced varied from 256 to 270 grams per square meter. These mats were compacted to a thickness of 20 to 30 mils.

EXAMPLE 2 A polypropylene nonwoven mat produced according to Example 1 was passed over a backup plate having an arc of approximately 2 to 6 inches radius. Directly over the arc was a die having equally spaced holes and fed by an extruder to force through the holes strands of polypropylene and a foaming agent, 1,1 azobisformamide (azodicarbonamide). Polypropylene (99.75 percent by weight) was mixed with the foaming agent (0.25 percent by weight), preferably with minor amount of white oil and aid in mixing the small amount of foaming agent throughout the pellets of polypropylene, and extruded at a temperature of 420 F. at a rate of 0.5 lbs./hr./hole with the nonwoven mat speed of 25 ftJmin. The strand of extrudate was 40 mils and has a density of 0.61 grams/cc. The nonwoven mat and extrudate were passed through calender rollers so that after passing through the fixed gap the dimensions of the extrudate ribs were about 0.030 inch high and 0.048 inch wide.

The foregoing examples are illustrative of the present invention in that polystyrene or blends of polypropylene and polystyrene have been melt-blown to produce mats which were compacted into suitable battery separators in the same manner as the polypropylene nonwoven mats of the examples. Likewise, a different thermoplastic may be extruded onto the nonwoven mat to provide the extruded ribs.

The nature and object of the present invention having been completely'described and illustrated and the best mode thereof contemplated set forth, what I wish to claim as new and useful and secure by Letters Patent 1. A method for forming a ribbed battery separator by extruding ribs on a nonwoven mat which comprises:

passing a nonwoven mat composed of randomly laid polypropylene, polystyrene,or mixtures thereof, fibers having an average diameter of less than 10 microns and having a maximum pore size of less than 40 microns over a backup plate having a portion which follows an arc, and

extruding a foamed molten polyolefin selected from the group consisting of polypropylene, polystyrene or mixtures thereof through a multi-hole die onto said nonwoven mat which is directly over said are portion of said backup plate to prevent shrinkage and to produce extruded polymer ribs on said mat, subsequently compressing said ribbed mat in a fixed gap to a thickness of 10 to 40 mils to produce said ribbed battery separator.

6 2. A method according to claim 1 wherein said nonwoven mat is first passed through a pair of fixed gap woven mat is made of polypropylene fibers. calender rolls.

3. A method according to claim 2 wherein said mol- 5. A method according to claim 1 wherein said fixed ten polyolefin is polypropylene. gap is a pair of calender rolls.

4. A method according to claim 1 wherein said non- 5 

2. A method according to claim 1 wherein said nonwoven mat is made of polypropylene fibers.
 3. A method according to claim 2 wherein said molten polyolefin is polypropylene.
 4. A method according to claim 1 wherein said nonwoven mat is first passed through a pair of fixed gap calender rolls.
 5. A method according to claim 1 wherein said fixed gap is a pair of calender rolls. 